4-methyl-8,8-dichloro-3,5-dioxabicyclo<5.1.0>octane | 58310-75-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧环庚烷
• 英文名称: 4-methyl-8,8-dichloro-3,5-dioxabicyclo<5.1.0>octane
• CAS: 58310-75-1
• 化学式: C₇H₁₀Cl₂O₂
• 分子量: 197.061
• InChiKey: JWUFJPDDDZWREZ-STNDOWJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-methyl-8,8-dichloro-3,5-dioxabicyclo<5.1.0>octane 在 蒽 、 四丁基碘化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  Role of Ni(II) and Co(II) ions in the mediated reduction of gem-dichlorocyclopropanes

  摘要：

  A study has been made of the influence of Co(II) and Ni(II) ions on the kinetics of the homogeneous reduction of gem-dichlorocyclopropanes by anthracene anion radicals. It has been shown that Co(II) and Ni(II) ions accelerate this process. The observed effect depends on the nature and concentration of the metal ion and also on the type of gem-dichlorocyclopropane. Two mechanisms are examined: 1) homogeneous reduction of metal ions by anthracene anion radicals with the formation of univalent and zero-valent metals that are more effective reducing agents; and 2) activation of a dichlorocyclopropane molecule by previous coordination with a metal ion.

  DOI：

  10.1007/bf00869504
• 作为产物：
  描述：

  2-methyl-4,7-dihydro-1,3-dioxepine 、 氯仿 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 反应 144.0h， 生成 4-methyl-8,8-dichloro-3,5-dioxabicyclo<5.1.0>octane 、
  参考文献：
  名称：

  Stereochemistry of Seven-Membered Heterocycles: XLIII. Steric Structure of Diastereoisomeric 8,8-Dichloro(dibromo)-4-R-3,5-dioxabicyclo[5.1.0]octanes

  摘要：

  Dichloro- and dibromocyclopropanation of 2-substituted 1,3-dioxacyclohept-5-enes according to Makosza resulted in formation of the corresponding 4-substituted 8,8-dichloro(dibromo)-3,5-dioxabicyclo[5.1.0]octanes in good yields. Ultrasonic activation of the process considerably shortened the reaction time. According to the C-13 NMR spectra, the chair-twist equilibrium is essentially displaced toward the chair conformer for the exo isomers and toward the twist conformer for the endo structures. Similar results were obtained by AMI semiempirical calculations which indicated that the (CClO)-O-... interaction largely determines the conformational equilibrium. The state of the diastereoisomer epimerization equilibrium depends on the size of the substituent at the acetal carbon atom.

  DOI：

  10.1023/b:rujo.0000003198.64663.ac

文献信息

• Stereochemistry of Seven-membered Heterocycles: XLIV. Spatial Structure of 4-R-3,5-Dioxabicyclo[5.1.0]octanes
  作者：V. Yu. Fedorenko、R. N. Baryshnikov、B. I. Khairutdinov、R. M. Vafina、Yu. G. Shtyrlin、V. V. Klochkov、E. N. Klimovitskii

  DOI：10.1007/s11178-005-0160-8

  日期：2005.2

  4-R-3,5-Dioxabicyclo[5.1.0]octanes were prepared in good yields by reduction of the corresponding 8,8-dichloro derivatives in a system Li-t-BuOH. According to the data of dynamic 1H and 13CNMR spectroscopy involving experiments in the NOESY mode the formal (R = H) at −93°C in (CD3)2CO exists in nearly equally occupied chair forms with endo- and exo-oriented three-membered ring. The like structure were found in the diastereomeric 4-Me(t-Bu)-analogs. The characteristic feature of 13C NMR spectra consists in considerable difference in the chemical shifts of the C8 atoms (Δδ∼16–17 ppm). The data on epimerization of diastereomers and calculations along AM1 procedure suggest for formal a three-component equilibrium including a twist-form.

  通过在 Li-t-BuOH 体系中还原相应的 8,8-二氯衍生物，制备了 4-R-3,5-二氧杂环[5.1.0]辛烷，并获得了良好的产率。根据动态 1H 和 13CNMR 光谱在 NOESY 模式下的实验数据，(CD3)2CO 中的形式（R = H）在-93°C 时几乎以内向和外向三元环的均等占位椅型存在。在非对映的 4-Me(t-Bu)-类似物中也发现了类似的结构。13C NMR 光谱的特点是 C8 原子的化学位移差异很大（Δδ∼16-17 ppm）。非对映异构体的表聚化数据和按照 AM1 程序进行的计算表明，正式的三组分平衡包括一种扭转形式。